Quick curing neoprene cement



Patented Sept. 4, 1945 UNITED STATES" PATENT OFFICE QUICK cuamdnaorauss cmms'r Louis S. Bake, Penna Grove, N. 1., asslgnor to E. I. du Pont de Nemours &: Company, Wilmingto DeL, a corporation of Delaware No Drawing. Application August 12, 1941,

a Serial No. 408,535

Clalms, ((1260-82) This invention relates to the curing of neoprene. More specifically, the invention relates to I absence of high temperatures is essential or de-' These objects have been accomplished by the discovery that the addition of sulfur chloride accomplishes the desired curing acceleration. It

has further been discovered that the addition of a small amount of an alcohol or a ketone to a neoprene composition containing sulfur chloride preserves the composition without materially delaying curing under conditions of use.

This invention is applicable to neoprene," a

generic term used to include products made by polymerizing .chloroprene (2-chloro-l..3-hutadiene) either in the presence or absence of modifiers, such, for example, as sulfur. It is especially valuable with neoprene of a type having sulfur in I chemical combination with the polychloroprene,

made by polymerizing chloroprene, in the presence of elementary sulfur, the efiect of the sulfur chloride being more marked with this type. The sulfur may amount to as much as is soluble in the chloroprene; i. e., up to about 2 per cent of the weight oi the chloroprene. This material is hereinaiter referred to" as sulfur-neoprene." polymerization is preferably carried out in emulsion. Emulsifying agents, antioxidants, agents for controlling polymerization rate, etc;, may be used all as known in the prior art. Although not preferred, massive or solution polymerizationmay be used.

In order that the processes of preparing polymeric materials especially suitable for the present The Onev and five-tenths (1.5) parts of sulfur was dissolved in 100 parts of chloroprenebyfirst dissolving the sulfur in 3 parts of a chlorinated naph-.

thalene having a. melting point 01 90 C. to 95 C. at 125 C. and stirring this hot solution into the chloroprene in which 4 parts of wood rosin had already been dissolved at C. This solution was then emulsified in 233 parts or water containing 0.5 part of ammonium persulfate, 0.5 part of the sodium salts of the dinaphthylmethane .sultonic acids prepared according to U. S. Patent No. 1,191,480 and 0.8 part of sodium hydroxide. The resulting dispersion was then maintained at 40 0., by cooling and heating as necessary, until the density reached 1.050. At this point, the dispersion was treated with 1 part of' phenyl-betanaphthylamine dispersed in sodium abietate solution, neutralized with acetic acid, and coagulated in the form of a continuous sheet as described in-the U. 3. Patent No. 2,187,146 to Calcott and Starkweather, by freezing it in a thin layer on the surface of a rotating, internally cooled drum, allowing the thin layer to remain in contact with the freezing surface for a length of time such that, on removing the film from the drum and allowing the ice therein to melt, a continuous sheet of completely coagulated material remained. The sheet was then washed by passing it under sprays of water while supported on a moving belt and dried by passage through a chamber through invention may be more fully understood, the 101- which air heated to C; was passing. Four per cent (4%) of tetramethyl thiuram disulfide was then incorporated into the dry polymer by milling and the product was then ready for storage,

Peocrss B A olymer was prepared according to the process of Process A except that 2 per cent of sulfur was used.

PROCESS C Chloroprene parts) was emulsified in a solution made by dissolving 5 parts of the sodium salts oi'sultated oleyl acetate, 0.5 part of sodium thioglycolate, and 0.2 part of sodium hydrosulilde (NaHS) in 188 parts of water and acidifying with hydrochloric acid to liberate the thioglycolic acid and hydrogen sulfide. The resulting dispersion was maintained at 40 C. until the density had increased to a point indicating that 95 per cent of the chloroprene had polymerized. A dispersion of 0.5 part of phenyl-beta-naphthylamine and 0.5 part of tetramethyl thiuram disulflde in 6 parts of water containing a small amount or the above sulfated oleyl acetate sodium salts was then added.

Qne hundred and eighty parts of this latex-likeidisper'sion was treated with a tation ited thereto as will appear more fully hereinafter.

Exam I A base cement was made by mixing together the following:

Base cement Parts Sulfur-neoprene made according to Process A 100 Heragethylene-ainmonium-hexamethylene-ditbiocarba- 1 Phenyl-beta-naphthylamine 2 Zinc oxide 6 Carbon black 50 Solvent 300 When 2 parts of sulfur chloride are mixed with 100 parts of the above base cement, a mixture is obtained, which, when brushed onto a supporting surface, will dry and become cured at ordinary room temperatures in approximately '72 hours. Quicker curing may be obtained by subjecting the film to elevated temperatures.

EXAMPLE II A plastic composition having a consistency similar to that of putty is prepared according to the following formula:

Base composition Parts Suliur-neoprene made according to Process A Diortho-ic yl-guanidinc Magnesium oxide swaxs Blane flxe Chlorinated dipbenyl To 100 parts of the above base composition is added a paste of the following composition:

Parts Sulfur chloride Chlorinated diphenyl 5 Elana fiXe The resultant productstays workable for several hours and becomes cured to an elastic, non-plastic body in approximately 24 hours at room temerature.

Exmurnn m A base cement was made by mixing together the following:

Base cement Parts Neoprene made according to Process C 100 Hexamethylene-ammonium-hexametbylene-dithiocarba- 1 mate Phenyl-beta-naphthylamine 2 Zinc oxide 5 Carbon ack 50 Solvent 294 Wheniu'l parts of sulfur chloride was mixed with 100 parts of the above cement it gelled in 6minutes. Five (5) parts ofethyl alcohol inh bited gelation. When a film of 100 parts of the above ccceptors.

ment containing 1.! parts of sulfur chloride and 5 parts of ethyl alcohol was brushed upon a supporting surface, it was cured in 5 days at room temperature. A similar film without the sulfur chloride and alcohol did not cure under these conditions.

The amount of sulfur chloride may, in general, vary from 0.1 to 35 parts to parts of the neoprene depending upon the desired time of workability and curing. It is impracticable to use over 35 parts of sulfur chloride per 100 parts of neoprene as curing with larger amounts takes place so rapidly that the time of workability is too short for practicable purposes.

Although the sulfur chloride is preferably intimately mixed with the base composition, this is not essential. Thus, the base cement of Example I may be brushed onto a supporting surface and allowed to dry to an uncured film. Sulfur chloride may then be applied to the film either alone or in a solution of an organic solvent such as benzene or carbon tetrachloride. This procedure vulcanizes the film only to the depth of the sulfur chloride penetration, thus producing a film having a cured outer surface and a soft uncured inner surface next to the supporting material whereby improved adhesion is obtained. This same procedure may be adapted in compositions similar to that disclosed in Example II where it is desirable to have a cured surface with a soft plastic, non-cured material beneath; for example, in certain types of caulking or crack-filling operations.

In the use of sulfur chloride for curing neoprene according to the present process, it is highly desirable that the composition contain an acid acceptor which will neutralize any acid formed during the curing step. Zinc oxide and magnesium oxide are examples of suitabl acid ac- In the first example of this specification, the amount of zinc oxide present is suilicient to render the composition neutral to litmus. It is desirable to point out that the neoprene composition itself is quite satisfactory in the absence of an acid acceptor because the acid does not have a seriously deleterious effect upon the neoprene. However, as will be pointed out more fully below, the composition of the present invention is very useful for coating materials which would be corroded or rotted by acid and the acid acceptor acts to preserve the material in contact with which the composition is to be used.

Neoprene cements having added sulfur chloride tend to gel rapidly: thus, if 1.8. grams ofsulfur chloride are added to 100 grams of the base cement of Example I, gelation occurs in approximately 4 hours, after which the compound is useless for brushing or dipping. It is, therefore, desirable that the composition contain a material which will stabilize it against gelation. It has been found that the addition of a small amount of an alcohol or ketone, volatile at the curing temperature, for example, methyl, ethyl and amyl alcohols. acetone, etc., prevent gelation. The amount of alcohol is not critical, but, in eneral, a few per cent of alcohol is sumcient. When the composition is used as a coating, adhesive, or impregnating composition, the alcohol or ketone evaporates and the curing occurs as though the alcohol or ketone had never been present. Ethyl alcohol is preferred. Alcohols and ketones having not more than 5 carbon atoms are especiallysuitable for the purpose.

Mixtures of alcohols, mixtures of ketones, or

to heat to cause mixtures of one or more alcohols with one or more ketones' can be used. in tact, under some circumstances, it may be advantageous to have both an alcohol and a ketone present, as, for example, ethyl alcoholand acetone.

The consistency of the composition may be varied by the use of greater or lesser amountspf solvent. In general, cements range from about 10 per cent to about 65 per cent sulfur-neoprene and putties range from about 65 per cent to about 85 per cent sulfur-neoprene. Any inert volatile organic solvent may be used, such, for example, as benzene, toluene, xylene. carbon tetrachloride, trichioromethane, etc. The solvent of Example I was a mixture of xylene and "Solveso No. l (a hydrogenated Substitute for toluene).

Conventional compounding ingredients for rubber and rubber-like materials may be present in the composition; also fillers, pigments, eto., such as are found in coating, caulking, and molding compositions. Depending upon the consistency and compounding ingredients, the herein disclosed compositions have many uses. They may be used as adhesives, for leather, wood, fab ric, metal, and other materials; as coating for chemical processing and storage equipment to prevent corrosion; as an impregnating composition for porous material such as corlr, fabric, wood, etc; as a veneer over rubber articles to protect them from sunlight, oxidation, or other deleteriow influences; and as a bonding agent for cornmlnuting material such as abrasives, cork dust, corl: granules, leather wrap, asbestos, etc. Plastic compositions may he used for the protection of steel or Wood equipment or pipe surfaces or, in fact, W material where it is impracticable oi? the'coating composition. Where the use of heat is not objectionable, the compositions are especially useful where it is desired to shorten the curing time. Thus, at l21 6., thin films containing 1 part of sulfur chloride per its parts of base or ment may he cured in about minutes. The plastic composh tions are also suitable for caulking as acid-resistant mortar, for setting up bricks in chemical equipment, etc, covering floors, decks, and steps. ieecause or the fact that the composition may be cured at or above ordinary room temperatures in short periods oi time. it can he used on large pieces of equipment which could not be easily rented or which, in fact, it would be impossible to raise the curing temperatures oi prior art compositions.

The contents made according to the present invention not only have the advantage or quick curing at low temperatures, but also have irn= proved hotly. Thus. 2 or 3 coats oi these cements give good hands where a much larger number of coats of other cements are frequently necessary. The following examples where "parts mean parts by weight illustrate this feature.

Exam A Adhesion of cured neoprene to itself Two (2) strips of cured neoprene composition (8" x l") were adhered together as follows:

The neoprene surface was roughened with sand paper and given 1 coat each of the accelerated .neoprene cement described in Example I. After drying for 2 hours, the strips were rolled together and heated for 18 hours at '70" C. A pull of 24 pounds per linear inch was required to strip the films.

. Exuums B Y Adhesion of cured rubber to itself Rubber test pieces were prepared and the films adhered as above in Example A. A pull of 22 pounds per linear inch was required to separate the film.

' Exaurrn C Adhesion of cured neoprene to cured rubber Test pieces were prepared and the films adhered as in Example A. A pull of 23 pounds was Gil required tostrip the LE D Adhesion oj-cured rubber to steel The metal was sand blasted and elven 1 coat of a priming cement having the following. composition:

Fourteen (14) parts 05: part A are mixed with 69 parts or P rt B.

This priming cement coating was followed by one coat or the cement described in Example I. The cured rubber was roughened and given 1 coat or neoprene cement of mample 1". After drying for 2 hours at room temperature, the was rolled into intimate contact with the cement on the metal and heated for 18 hours at 76 fi. A pull of 25 pounds per linear inch was required to strip the film fr the metal.

Example E Adhesion of cured neoprene to steel Test pieces were prepared and treated as in mample D using cured neoprene in place or cured rubber. A pull of 21 pounds per linear inch was required to strip the film from the metal.

It is apparent that many widely difierent em= hodiments of this invention may be made with= out departing from the spirit and scope thereof, and, therefore, it is not intended to be limited except as indicated in the appended claims.

I claim:

l. A relatively rapid, low temperature curing polychloroprene composition comprising a mix ture of uncured polychloroprene, from 0.1% to 35% of sulfur chloride, based on the weight of the polychloroprene, a volatilizable liquid of the class consisting of alcohols and iretones which contain less than six carbon atoms, and an inert volatile )rganic solvent. I

2. A relatively rapid, low temperature curing polychloroprene composition comprising a mix ture of uncured pulychloroprene, from 0.1% to 35% of sulfur chloride, based on the weight of the polychloroprene, a volatilizable liquid of the class consisting of alcohols and ketones which contain less than six carbon atoms, an acid acceptor, and. an inert volatile organic solvent.

3. A relatively rapid, low temperature curing polychloroprene composition comprising a mixture of uncured polychloroprene obtained by polymerizing chloroprene in the presence of an amount of elementary sulfur up to 2% of the weight of the chloroprene, from 0.1% to 35% of sulfur chloride, based on the weight of the polychloroprene, a volatilizable liquid of the -class consisting of alcohols and ketones which contain less than six carbon atoms, and an inert volatile organic solvent.

4. A relatively rapid. low temperature curing polychloroprene composition comprising a mixture of uncured polychloroprene obtained by polymerizing chloroprene in the presence of an amount of elementary sulfur up to 2% of the weight of the chloroprene. from 0.1% to 35% of sulfur chloride, besed'on the weight of the polychloroprene, ethyl alcohol, and an inert volatile organic solvent.

5. A relatively rapid, low temperature curing .polychloroprene composition comprising a mix- 

